Data from: High-throughput generation of block copolymer libraries via click chemistry and automated chromatography
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Oct 06, 2025 version files 62.48 MB
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EAMurphy_High-Throughput.zip
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README.md
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Abstract
Designing block copolymers for specific applications is challenging because of the intricate relationship among molecular structure, self-assembly behavior, and bulk properties, which is compounded by a large design space that traditionally requires time-consuming, iterative synthesis. To overcome these challenges, here we report a library-based strategy leveraging an active ester-based block copolymer and automated chromatography which enables the high-throughput exploration of broad compositional and chemical landscapes without requiring sample-specific optimization. By integrating automated chromatography with robotic synthesis and orthogonal post-polymerization modification chemistry, we efficiently generated a diverse library of 90 well-defined block copolymers from a single as-synthesized “parent” copolymer. This adaptable method enables efficient access to materials with a wide range of compositions, molecular weights, functionalities, and properties. By integrating laboratory automation with click chemistry, these insights will accelerate the discovery and design of advanced block copolymers for high-performance applications.
High-Throughput Generation of Block Copolymer Libraries via Click Chemistry and Automated Chromatography
Elizabeth A. Murphy,†,‡,# Katherine G. Roth,‡ Morgan W. Bates,# Megan C. Murphy,†,‡ Jerrick Edmund,†,§ Christopher M. Bates,†,‡,%,# and Craig J. Hawker,†,‡,%,#
†Materials Research Laboratory, ‡Department of Chemistry & Biochemistry, %Materials Department, §Department of Chemical Engineering, and #BioPACIFIC Materials Innovation Platform, University of California, Santa Barbara, California 93106, United States
Macromolecules 2025, 58, 15, 8369–8376
Data file names are labeled as Sample Name_Characterization Technique and organized into folders corresponding to figure and table numbers in the manuscript.
Data is acquired from the following analytical characterization techniques. Details of the experimental design and data are highlighted below:
Nuclear Magnetic Resonance Spectroscopy: Solution state nuclear magnetic resonance (NMR) spectra were recorded on a Varian 600 MHz spectrometer. Chemical shifts (δ) are reported in ppm relative to residual protio-solvent in CDCl3 (7.26 ppm). 1H, 13C, and 19F data has been collected. Data is shown as x column: chemical shift (ppm) and y column: intensity (a.u.). Data is in a .csv format.
Size Exclusion Chromatography: Size-exclusion chromatography (SEC) was conducted on a Waters Alliance HPLC System, 2690 Separation Module using chloroform with 0.25% triethylamine as the eluent with a flow rate of 0.35 mL/min. Refractive index traces from a Waters 2410 Differential Refractometer detector were used for estimates of the molar mass and dispersity relative to linear polystyrene standards with a chloroform mobile phase. Data is shown as x column: retention time (min) and y column: differential refractive index intensity (arb. units). Data is in a .txt format.
Small Angle X-Ray Scattering: SAXS measurements of bulk samples were conducted using a custom-built high brilliance laboratory beamline for small and wide angle X-ray scattering (SAXS/WAXS) at the BioPACIFIC Materials Innovation Platform at University of California, Santa Barbara. The instrument is constructed using a high brightness liquid metal jet X-ray source (D2+ 70 kV from Excillum), a low background scatterless slit beam collimation system developed in house, and a 4-megapixel hybrid photon counting area detector (Eiger2 R 4M from Dectris) housed inside a 3 meter-long vacuum vessel. Data is shown as x column: scattering q vector (A-1), y column: intensity (a.u.), and z column: error. Data is in a .txt format.
Differential Scanning Calorimetry: Differential scanning calorimetry (DSC) was performed using a TA Instruments DSC Q2000 from –90 to 55 °C at a heating/cooling rate of 10 °C/min using 3–5 mg of sample in a sealed Tzero aluminum pan. Data is shown as x column: time (min), y column: temperature (ºC), and z column: heat flow (W/g). Data is in a .txt format.
Thermogravimetric Analysis: Thermogravimetric analysis (TGA) was performed under argon from 50 to 700 ºC on a TA Instruments Q500 at a heating rate of 10 ºC/min. Data is shown as first column: time (min); second column: temperature (ºC); third column: weight (mg); fourth column: weight percent (%) . Data is in a .txt format.
Fourier Transform Infrared Spectroscopy: Fourier-transform infrared (FTIR) spectroscopy measurements were performed on a Thermo Nicolet iS10 FTIR spectrometer equipped with a Smart Diamond attenuated total reflectance (ATR) accessory. A background spectrum was obtained every 30 minutes and sample spectra were taken with 64 scans in absorbance and transmittance mode. Data is shown as x column: absorbance or transmittance (arb. units) and y column: wavenumber (cm-1). Data is in a .txt format.
Mass Recovery and Gradient Elution Data from Automated Chromatography: Automated flash chromatography was performed on a Biotage Selekt unit installed with an external evaporative light scattering detector (ELSD), using Biotage Sfär cartridge series (200 g) eluted with suitable hexanes/ethyl acetate solvent gradients. All chromatographic solvents were ACS grade or better and used without further purification. In fractionation experiments, the mass recovery was taken as the ratio of the collected mass to the injected mass. Mass recovery data is shown as x column: test tube number and y column: mass (mg). Data is in a .txt format.
All data presented in the main text of the manuscript can be found in the folder titled “Main Manuscript.” For detailed information about each dataset, please refer to the corresponding analytical characterization technique sections described above.
Figure 3: Size-exclusion chromatograms (SEC) of poly(ethyl acrylate)-b-poly(tetrafluorophenyl acrylate) diblock copolymer and precursors.
Figure 4: 1H NMR spectra of the precursor poly(ethyl acrylate) homopolymer, E-TTC, and poly(ethyl acrylate)-b-poly(tetrafluorophenylacrylate) diblock copolymer before, EF-TTC, and after, EF-H, chain-end removal.
Figure 5a: Mass recovery data. Chromatographic separation of a parent active ester diblock copolymer on a ≈11 g scale afforded a large library of fractionated samples with high mass recovery of 67%.
Figure 5b: 1H NMR data to highlight volume fraction changes of fractions throughout the separation.
Figure 7: 1H NMR data. Examples of distinct diblock copolymers obtained from a single as-synthesized parent material as evidenced by 1H NMR spectroscopy.
Figure 8: Size-exclusion chromatograms of a representative block copolymer derived from a single chromatographically separated fraction indicate efficient functionalization with primary amines.
Figure 9: Differential scanning calorimetry thermograms (exo up, second heating cycle) of a representative block copolymer derived from a single fractionated sample. Representative thermograms are shown of the fractionated active-ester diblock copolymer and thiophene-2-ethylamine based diblock copolymer derived therefrom.
All data presented in the supporting information of the manuscript can be found in the folder titled “Supporting Information.” For detailed information about each dataset, please refer to the corresponding analytical characterization technique sections described above.
Figure S1: 1H NMR in CDCl3 of 2,3,5,6-tetrafluorophenyl acrylate monomer using a 400 MHz NMR spectrometer.
Figure S2: 1H NMR with fluorine decoupling in CDCl3 of 2,3,5,6-tetrafluorophenyl acrylate monomer using a 400 MHz NMR spectrometer.
Figure S3: 13C NMR in CDCl3 of 2,3,5,6-tetrafluorophenyl acrylate monomer using a 400 MHz NMR spectrometer.
Figure S4: 19F NMR in CDCl3 of 2,3,5,6-tetrafluorophenyl acrylate monomer using a 400 MHz NMR spectrometer.
Figure S5: FTIR spectrum of 2,3,5,6-tetrafluorophenyl acrylate monomer.
Figure S6: 19F/1H heteronuclear correlation spectroscopy of 2,3,5,6-tetrafluorophenyl acrylate monomer using a 400 MHz NMR spectrometer.
Figure S7: 19F/13C heteronuclear single quantum coherence of 2,3,5,6-tetrafluorophenyl acrylate monomer using a 400 MHz NMR spectrometer.
Figure S8: 19F/13C heteronuclear multiple bond correlation of 2,3,5,6-tetrafluorophenyl acrylate monomer using a 400 MHz NMR spectrometer.
Figure S9: 1H NMR of poly(tetrafluorophenyl acrylate) homopolymer using a 600 MHz NMR spectrometer.
Figure S10: . FTIR spectrum of poly(tetrafluorophenyl acrylate) homopolymer.
Figure S11: 19F NMR of poly(ethyl acrylate)-b-poly(tetrafluorophenyl acrylate) with trithiocarbonate and proton chain end using a 600 MHz NMR spectrometer.
Figure S14: Mass recovery data. Recovered mass was combined into 18 distinct fractions with masses between ~400 –500 mg to have sufficient material for robotic functionalizations.
Figure S15: 1H NMR spectra of as synthesized parent poly(ethyl acrylate)-bpoly(tetrafluorophenyl acrylate) diblock copolymer and a representative fractionated sample (fraction 79–83) using a 500 MHz NMR spectrometer.
Figure S16: 19F NMR spectra of as synthesized parent poly(ethyl acrylate)-bpoly(tetrafluorophenyl acrylate) diblock copolymer and a representative fractionated sample (fraction 79–83) using a 500 MHz NMR spectrometer.
Figure S17: Size-exclusion chromatograms (normalized differential refractive index signal, dRI) of fractionated poly(ethyl acrylate)-b-poly(tetrafluorophenyl acrylate) diblock copolymers.
Figure S18: Small-angle X-ray scattering patterns of fractionated poly(ethyl acrylate)-b-poly(tetrafluorophenyl acrylate) diblock copolymers.
Table S2: Molecular characterization data for well-defined fractionated diblock copolymers from parent poly(ethyl acrylate)-b-poly(tetrafluorophenyl acrylate). Data in table found in Figure S14 (mass recovery), Figure 5b (NMR data), and Figure S17 (SEC data) and is not duplicated.
Figure S19: Representative 19F NMR spectra of fractionated poly(ethyl acrylate)-b-poly(tetrafluorophenyl acrylate) diblock copolymer and 4-(trifluoromethyl)benzylamine functionalized sample derived therefrom using a 500 MHz NMR spectrometer.
Figure S20: Representative 19F NMR spectra of fractionated poly(ethyl acrylate)-bpoly(tetrafluorophenyl acrylate) diblock copolymer and its derivative functionalized with thiophene-2-ethylamine, 2-(4-chlorophenyl)ethylamine, and 4-methoxyphenethylamine (top to bottom) using a 500 MHz NMR spectrometer.
Figure S21: Representative size-exclusion chromatograms (normalized differential refractive index (dRI) signals) of a set of functionalized diblock copolymers. SEC chromatograms are shown for a complete series of 18 distinct 2-(4- chlorophenyl)ethylamine-functionalized diblock copolymers.
Figure S22: Size-exclusion chromatograms (normalized differential refractive index signal, dRI) of four functionalized block copolymers derived from a single fractionated sample (fraction 63–66). Chromatograms of amine-functionalized derivatives are shown in (a) orange for thiophene-2-ethylamine, (b) green for 4-(trifluoromethyl)benzylamine, (c) blue for 2-(4-chlorophenyl)ethylamine, and (d) purple for 4-methoxyphenethylamine.
Figure S23: TGA thermograph of poly(tetrafluorophenyl acrylate) homopolymer. Td5% is observed at 306 ºC.
Figure S24: DSC thermogram (exo up, second heating cycle) of poly(tetrafluorophenyl acrylate) homopolymer. Glass transition temperature is observed at 58 ºC.
Figure S25: TGA thermograph of poly(ethyl acrylate)-b-poly(tetrafluorophenyl acrylate) diblock copolymer (fraction 89–94). Td5% is observed at 304 ºC.
Figure S26: DSC thermogram (exo up, second heating cycle) of fractionated poly(ethyl acrylate)-b-poly(tetrafluorophenyl acrylate) diblock copolymer (fraction 84–88). Glass transition temperature is observed at 25 ºC.
Figure S27: TGA thermograph of thiophene-2-ethylamine functionalized diblock copolymer derived from fraction 84–88. Td5% is observed at 303 ºC.
Figure S28: DSC thermogram (exo up, second heating cycle) of thiophene-2-ethylamine functionalized diblock copolymer derived from fraction 84–88. Glass transition temperatures are observed at –10 ºC and 69 ºC.
Figure S29: TGA thermograph of 4-(trifluoromethyl)benzylamine functionalized diblock copolymer derived from fraction 84–88. Td5% is observed at 301 ºC.
Figure S30: DSC thermogram (exo up, second heating cycle) of 4- (trifluoromethyl)benzylamine functionalized diblock copolymer derived from fraction 84– 88.
Figure S31: TGA thermograph of 2-(4-chlorophenyl)ethylamine functionalized diblock copolymer derived from fraction 84–88. Td5% is observed at 279 ºC.
Figure S32: DSC thermogram (exo up, second heating cycle) of 2-(4- chlorophenyl)ethylamine functionalized diblock copolymer derived from fraction 84–88.
Figure S33: TGA thermograph of 4-methoxyphenethylamine functionalized diblock copolymer derived from fraction 84–88. Td5% is observed at 291 ºC.
Figure S34: DSC thermogram (exo up, second heating cycle) of 4-methoxyphenethylamine functionalized diblock copolymer derived from fraction 84–88. Glass transition temperatures are observed at –7 ºC and 85 ºC.
Figure S35: Small-angle X-ray scattering patterns of fractionated poly(ethyl acrylate)-b-poly(tetrafluorophenyl acrylate) diblock copolymer (fraction 84–88) and thiophene-2-ethylamine functionalized diblock copolymer derived from fraction 84–88.
Figure S36: Small-angle X-ray scattering patterns of fractionated poly(ethyl acrylate)-b-poly(tetrafluorophenyl acrylate) diblock copolymer (fraction 84–88) and 4-(trifluoromethyl)benzylamine functionalized diblock copolymer derived from fraction 84–88.
Figure S37: Small-angle X-ray scattering patterns of fractionated poly(ethyl acrylate)-b-poly(tetrafluorophenyl acrylate) diblock copolymer (fraction 84–88) and 2-(4-chlorophenyl)ethylamine functionalized diblock copolymer derived from fraction 84–88.
Figure S38: Small-angle X-ray scattering patterns of fractionated poly(ethyl acrylate)-b-poly(tetrafluorophenyl acrylate) diblock copolymer (fraction 84–88) and 4- methoxyphenethylamine functionalized diblock copolymer derived from fraction 84–88.